Hydroxymethylphosphines and process for preparing the same



United States Patent 3,243,450 HYDROXYMETHYLPHOSPHINES AND PROCESS FOR PREPARING THE SAME Martin Grayson, Norwalk, Conn., assignor to American Cyanamid Company, Stamford, Conn., a corporation of Maine No Drawing. Filed Dec. 26, 1963, Ser. No. 333,696

.. Claims. (Cl. 260465.6)

In 1930 A. Hoffman, Journal of the American Chemical Society, 52, 2995, disclosed the following reaction:

As taught in the equation, tris(hydroxymethyl)phosphine oxide is the principal Hotfman product.

Quite surprisingly, it has been found pursuant to the instant discovery that by proper control of conditions the hydroxymethyl phosphine derivatives of THPC, and the like, rather than the hydroxymethyl phosphine oxide derivatives, may be produced. According to the present invention a hydroxymethyl phosphonium salt of the formula is brought into reactive contact, in the presence of a member selected from the group consisting of water and a lower aliphatic alcohol, with a base, said base being present in the reaction mixture in an amount no greater than about a stoichiometric quantity throughout substantially all of the reaction; the corresponding hydroxymethyl phosphine having the formula is recovered; R and R in the above formulae represent members selected from the group consisting of branched and straight chain alkyl (C -C branched and straight chain alkenyl (C -C cycloalkyl, cycloalkenyl and phenyl; said alkyl, alkenyl, cycloalkyl, cycloalkenyl, and phenyl moieties being substituted or unsubstituted, as will be seen hereinafter; R and R may be the same or different; x is selected from 0 land 1; y is selected from 0 and l; and Y is a mineral acid residue, i.e., a mineral acid anion.

Pursuant to a further embodiment of the present invention a hydroxymethyl phopshine of the formula R P(CH OH) and an alkyl (C -C halide of the formula RI'X are brought into reactive contact and the corresponding hydroxymethyl phopshine halide recovered, said halide having the formula [R"R P (CH OH) X R in the latter two formulae represents a member selected Patented Mar. 29, 1966 from the group consisting of branched and straight chain alkyl (C -C branched and straight chain alkenyl (C C cycloalkyl, cycloalkenyl, phenyl; said alkyl, alkenyl, cycloalkyl, cycloalkenyl and phenyl moieties being substituted or unsubstituted, as will be seen hereinafter; R" is alkyl from 1 to 20 carbon atoms; X is halogen; and q is selected from 0, 1, and 2.

A wide variety of temperatures may be employed in each of the reactions just given. Best results are obtained at a temperature in the range of 20 C. to 100 0., preferably 0 C. to C.

Typical bases within the purview of the present discovery are the oxides, hydroxides, lower alkoxides and carbonates of alkali metals and alkaline earth metals. Included among these are, for example, NaOH, Na CO NaHCO CaO, BaO, NaOC H NaOC H-;i, and the like. Generally these bases are present in a concentration sufiicient to provide a final H ion concentration in the range of pH 4 to pH 9. Other bases within the purview of the instant discovery are tertiary alkyl amines, tertiary aralkyl amines and tertiary heterocyclic amines, such as triethylamine, N,N-dimethylaniline, pyridine, and other similar strongly basic organic tertiary amines.

As indicated hereinabove, the bases are present in the reaction mixture in an amount no greater than about a stoichiometric quantity throughout substantially all of the reaction, based on the phosphonium salt reactant. Best control of concentration may be had by simply adding the base to the phosphonium salt reactant, thus permitting a stoichiometric excess of the phosphonium salt throughout substantially all of the reaction. However, other methods of admixing the reactants are contemplated, such as impinging streams of reactants, and the like.

The solvents contemplated herein are selected from the group consisting of water and lower alkyl alcohols such as methanol, ethanol, propanol, isopropanol and butanol. It has been found that when a lower alkyl alcohol is used as a solvent, the method of addition of the reactants is not as critical; however, best results are achieved by adding the base to the phosphonium salt and maintaining the base concentration in an amount no greater than about stoichiometric quantity, based on the phosphonium salt reactant.

The embodiment discussed hereinabove wherein a hydroxymethyl phosphine of the formula R P CH 0H) is reacted with an alkyl halide (RX) is not restricted to any particular sequence of addition and is generally carried out in the presence of an inert organic solvent, such as water, lower alkanols, and other inert organic polar solvents, such as acetonitrile, and the like. The ratio of reactants, likewise, is not critical and is governed only by practicality and ease of operation.

All of the reactions contemplated herein may be car. ried out in batch, continuous or semi-continuous processes. By the same token, while good results are achieved at atmospheric pressure, super-atmospheric and sub-atmospheric pressures are contemplated.

Hydroxymethyl phosphines corresponding to the formula x y 4- (x-l-y) eaYe above, wherein R and/or R are phenyl, substituted or unsubstituted, and Y is halogen may be prepared by reacting the corresponding substituted or unsubstituted phenylphosphine or diphenylphosphine with formaldehyde and a hydrohalide in the presence of water according to the following equation:

3 Wherein R and R represent phenyl, substituted or unsubstituted, Y is halogen and x and y have the meanings given above.

This reaction is carried out at a temperature in the phosphine oxide contaminant. Treatment with excess methyl iodide gives a syrupy methiodide; calculated for C H PO I: I, 47.70. Found I, 47.2.

Example lII.-Bis(hydroxymethyl)methylphosphine range of C. to 50 C., in a batch, continuous or semi- 5 continuous manner, and at sub-, superor atmospheric A SOIHUOII 0f -6 g ams (0.10 mole) of tris(hydroxypressures, methyl)methylphosphoniurn iodide in 75 milliliters of The present invention ill be t be und r tood by irt absolute ethanol is allowed to react under nitrogen with f the f ll i examples; a solution of 2.3 grams (0.10 grain atom) of sodium in 75 milliliters of absolute ethanol at 0 C. No gases are 10 Example T(hyd'oxymethynphosphme produced and the residual liquid, after removal of sol- Purified tetrakis(hydroxymethyl)phosphonium chloride vent and inorganic salts, gives an infrared spectrum sim- (TI-IPC, 2.0 grams, 0.01 mole) of melting point 149 C. ilar to that of tris(hydroxymethyl)phosphine with the 150 C. is dissolved in 30 milliliters of absolute ethanol addition of methyl group absorptions. This residue has and 0.45 gram (0.01 mole) of sodium hydroxide dis- 5 boiling point 67 C.-69 C. at 0.5 millimeter of mercury solved in milliliters of absolute ethanol is added all and is identified by molecular weight and mass spectroat once at ambient temperature (23 C.) in a nitrogen metric analysis as bis(hydroxymethyl)methylphosphine. atmosphere with stirring. No gases are evolved but the E xam le IV. H dox m h len l precipitated sodium chloride is filtered and the filtrate y r y er yndlp 1 ylplfosp une stripped of solvent (in the absence of air) to a residual 20 A S01l1t 10I1 0f g 0f Y Y- fluid. The infrared absorption spectrum indicates absence y {P Y P P Chloride 1n loo'mlllllltel's of phosphine oxide groups and characteristic eaks eX- water 18 treated under nitrogen at 24 C. With a $0111- pected for tris(hydroxymethyl)phosphine. The residue U011 9 f grams mole) of SOdlllm hydroxide in is redissolved in ethanol d treated i h an h l 25 milliliters of water. After evaporation of water under solution of 1.1 grams 0.01 mole) of freshly crystallized 25 y the product y y p y p p benzoquinone The Orange adduct is l l is extracted from starting material and inorganic salts culated f C9-H13PO5; C 4 5 H, 5,6Q Found; C, with benzene and is separated from the extractant and 46.34, H, 4.40. purified.

Example II.Tris(hydroxymethyl)phosphine Example V-cyclohexylbis(hydloxymethyl)Phosphine A solution of 7.6 grams 0.04 mole) of THPC in 50 A Solution 1 e y y ifl y ymilliliters of Water at 28 C. is treated under nitrogen y )l p Chlofld? III 100 Inlllllltefs 0f with a Sohltioh f 1 grams 04 mole) f sodium butanol is allowed to react with a solution of 0.10 gram hydroxide in 25 milliliters of water in a period of 1-5 fltom Sodlum In 100 milliliters of n-blltanol minutes with stirring. No gas evolution is observed after In I11tr0gen at1n0SPheTe- After filtratlon 0f Insoluble stirring 2 hours at this temperature or after standing over- SOdlllm Phloflde and removal of Solvent y Vacuum night in the closed system. The water is removed by P Q the Product y y y y y pumping at C. C. and the residue is extracted P p 1S recoveredwith 50 milliliters of absolute ethanol to remove sodium Exam les VI XXHI chloride. The residue after removal of ethanol under 40 p nitrogen weighs 4.8 grams or 97 percent of theoretical The following examples are carried out in every esfor tris(hydroxymethyl)phosphine. Infrared analysis insential respect as in Example I, above, except as irididicates a substantially pure product, free of tertiary cated in Table I.

TABLE I [RXR P(CHzOH).i-(x+y)] Y base RxR P(CHiOH)a X+ Example Phosphoniiim salt Base Molar ratio, Solvent Temp., Product No. saltzbase C.

Tris(hydroxymethyl)methylphos- NaOH 1:1 2-propanol 23 Bis(hydroxy-methyl)methylphospine.

phonium iodide. Z-cyauoethyl-tris(hydroxymethyl)- Ca(OH) 1:1 H20 70 2-cyanoethyl-bls(hydroxymethyD- phosphonium bromide. phosphine. 3-buteriyl-tris(hydroxymethyl)phos- Triethylamine 1:1 Propanol. 29 3-butenyl-bis(hydroxymethyl)phosphonium bromide. phine. Bis(hydroxymethyl)dioctylphos- NaOCzHs 1:1 Butanol 23 Bis(hydroxymethyl)dioctylphosphine.

phonium sulfate. Dodecyl-tris(hydroxymethyl)phos- NaOi-Pr 1:1 Methan0l 20 Dodecyl-bis(hydroxy'methyDphosphonium phosphate. phine. 4-ethoxybutyl-tris(hydroxymethyD- CaO 1:1 H2O 25 4-eth0xybutyl-bis(hydroxymethyl)- phosphonium chloride. phospine. 3-hydroxycyclohexyl-tris(hydroxy- NaiCoa 1:1 Hi0 20 3-hydroxycyclohexyl-bis(hydroxymethyhphosphonium iodide. methyDphosphine. XIII Bis(3-cyclohcxenyl)-bis(hydroxy- N,N-dimethy1- 1:1 Ethanol... -10 Bis(3-cycl0hexeny1)hydroxymethylmethyl) phosphonium chloride. aniline. phosphine. XIV Tris(hydroxymethy1)octadecylphos- Pyridine 1:1 Butan0l 15 Bis(hydroxymethyl)octadecylphos- ,phom'um brom' e. phine. XV Bis(4chl0rophenyl)-bls(hydroxy- Na CO 1:1 Ethanol l0 Bis(4chl0r0phenyl)hydroxymethylmethyl) phosphonium chloride. phosphine. XVI Tris(hydroxymethyl)-4-methyl- BaO 1:1 H2O 30 Bis(hydroxymethyl)-4-methylpheny1- phenylphosphonium iodide. phosphine. XVII Bis(4-butoxyphenyl)-bis(hydroxy- NaHCO; 1:1 H2O 0 Bis(4bi1toxyphenyl)hydroxymethylmethyhphosphonlum chloride. phosp ne. XVIII 3-propoxyhexyl-tris(hydroxymethyD- 0&(OH); 1:1 Ethan0l 25 3'propoxyhexyl-bis(hydroxymethyD- phosphonium chloride. phosphine. XIX Tris(hydroxymethyl)-3-propylphenyl- Triethylamine 1:1 H2O 20 Bis(hydroxyrnethyl)-3-propylphenylphosphonium brom' e. phosphlne. XX 2-butylphenyl-tris(hydroxymethyl)- 1:1 Propan0l- 25 2-butylphenyl-bls(hydroxymethyl)- phosphonium iodide. phosphine. XXI Bis(4 fluorophenyl)-bis(hydroxy- NaOCzHs 1:1 Methanolun 23 Bis-(4-fiuorophenyl)hydroxymethylmethyDphosphonimn chloride. phosphine. XXII Bis(fi-bromophenyl)-bis(hydroxy- N,N-dimethyl- 1:1 Butanol 25 Bis(3-br0m0phenyl)hydroxymethylmethyl)phosphoniu m chloride. aniline. phosphine. XXIII i-ethoxyphenyl-tris(hydroxymethyl)- NazCO3 1:1 H2O 4-ethoxyphenyl-bis(hydroxymethyl)- phosphonium sulfate. phosphlne.

Examples XXIV-XXX VI The following examples illustrate the conversion of the hydroxymethyl phosphines contemplated herein to their corresponding phosphonium halides according to the equation:

of any of these phosphin'es or a mixture of these phosphines, such as tris(hydroxymethyDphosphine, hydroxymethyldiphenylphosphine, or the like, in one gallon of gasoline affords protection against misfiring, surface ignition and the like.

Clearly the instant discovery encompasses numerous modifications within the skill of the art. Consequently,

TABLE II Reactants Molar ratio, Example hydroxymeth- Solvent Temp, Product ylphosphine: C. Hydroxymethylphosphine Alkyl halide alkyl halide Tris(hydroxymethyl)phosphine 0211 01 1:1 Water 22 Ethyl-tris(hydroxymethyl)phosphonium chloride. XXV Bis(hydroxymethyl)methylphos- CgHflBr 1:1. 5 Ethanol Bis(hydroxymethyl)octylmethylphine. phosphonium bromide. XXVI (H ydroxymethyl) diphenylphos- 012111501 1. 5:1 Isopropanol- 30 (Hydroxyrnethyl) dodecyldiphenylphine. phosphonium chloride. XXVII. Cyclohexylbis(hydroxymethyl) CmHmOl 1: 1 Methanol. 4O Cyclohexylbis(hydroxymethyDoctaphosphine. decylphosphonium chloride. XXVIIL i-ethoxybutyl-bis(hydroxymethyl) C3H7Cl 1:1 Propanol 8 -ethoxybutyl-bis(hydroxymethyl) phosphine. propylphosphonium chloride. XXIX 2-cyan0ethyl-bis(hydroxymethyl) CHaI 1:1 Acetonitrlle..- 2-cyanoethyl-bis(hydroxymethyl) phosphine. methylphosphonium iodide. XXX Bis(hydroxymethyl)-3-propoxyhex- C H11I 1:1 Methanol- .r 35 Bis(hydroxymethyl)pentyl-3-propoxylphosphine. yhexylphosphonium iodide. XXXI Bis(hydroxymethyl)-3-propylphen- CHQC] 1. 5:1 Propanol 15 Butyl-bis(hydroxymethyl)-3-propylylphosphine. phenylphosphonium chloride. XXXII 2-butylphenyl-bis (hydroxymethyl) CHaCl 1:1 Isopropanol. 40 2-butylphenyl-bis(hydroxymethyl) phosphine. methylphosphonium chloride. XXXIII Bis(4-fiuorophenyl)hydroxymethyl- C1H Br 1:1 Ethanol Bis(4-flu0rophenyl)heptyl-hydroxyp osphine. methylphsophonium bromide. XXXV 3-bromophenyl-bis(hydroxymethyl) C5H Br- 1: 1 Methanol- 38 3-bromophenyl-bis(hydroxymethyl) phosphine. pentylphosphonium bromide. XXXVL Bis(4-ethoxyphenyl)hydroxymeth- C4H9C1 1:1 Ethanol 30 Butyl-bis(4-ethoxyphenyl)hydroxyylphosphine. methylphosphonium chloride.

Examples XXXVII-XLV The following examples illustrates the reaction of a hydrohalide, a substituted or unsubstituted phenylphosphine or diphenylphosphine according to the equation:

while the present invention has been described in detail with respect to specific embodiments thereof, it is not intended that these details be construed as limitations upon the scope of the invention, except insofar as they appear in the appended claims.

I claim:

1. A hydroxymethylphosphine having the formula TABLE III Reactants Example Molar Ratio Tempera- Product of Reactants ture, C. Phenylphosphine (EH 0 XXXVII Phenylphosphine CHzO 1:3:1 22 Tris(hydroxymethyl)phenylphosphonium chloride. XXXVIII Diphenylphosphine CHzO 1:211 22 Bis(hydroxymethyl)diphenylphosphonium chloride. XXXIX Bis(4-chlorophenyl)phosphine OHQO HBr 1:3:1 5 Bis(4-chlorophenyl)-bls(hydroxymethybphosphonium bromide. XL Bis(4-butoxyphenyl)phosphine CHilO HI 1:4:1 40 Bis(4-butoxypl1enyl)-bis(hydroxymethyDphosphonium iodide. XLI 4-methylphenylphosphme CHz HCI 1:3:1 10 Tris(hydroxymethyD-4-methyl- I phenylphosphonium chloride. XLII Bis(4-ethoxyphenyl)phosphme CH O H01 1:311 15 Bis(4-ethoxyphenyl)-bis(hydroxymethybphosphonium chloride. XLIII 3-propylphenylphosphine CHzO HBr 1:3:1 12 Tris(hydroxymethyl)-3-propylphenylphosphonium bromide. XLIV Bis(3-bromophenyl)phosphlne CH O HCl 1:3:1 35 Bis(3-bromophenyl)-bis(hydroxymethyl) phosphonium chloride. XLV Bis(4-fiuorophenyl)phosph1ne CH2O HCI 1:411 15 Bis(4-fluorophenyl)-bis(hydroxymethybphosphonium chloride.

It follows from the above examples that typical substituents, when R and R represent alkyl (C -C are cyano and lower alkoxy (C -C when R and R represent phenyl, typical substituents are lower alkoxy (C C lower alkyl (C -C and halo (e.g. Cl, Br and F); and when R and R represent cycloalkyl a typical substituent is hydroxy.

The hydroxymethyl phosphines R R' P(CH OH) prepared according to the present invention are useful as gasoline additives. For example, up to about 10 milliliters wherein R and R represent the same and different members selected from the group consisting of alkyl having from 1 to 20 carbon atoms; substituted alkyl having from 1 to 20 carbon atoms; alkenyl having from 2 to 20 carbon atoms; said substituents for alkyl being selected from the group consisting of cyano and lower alkoxy; cyclohexyl; hydroxy-substituted cyclohexyl; cyclohexenyl; phenyl; substituted phenyl; said substituents for phenyl being selected from the group consisting of lower alkoxy, lower alkyl and halo; x is selected from O and 1; y is selected from 0 and 1;

and the sum of x plus y is selected from 1 and 2.

7 2. Bis(hydroxymethyl)methylphosphine. 3. Z-cyanoethyl-bis (hydroxymethyl phosphine. 4. Bis (hydroxymethyl)-4-methylphenylphosphine. 5. 2-cyanoethyl bis(hydroxy methyl)methylphosphonium chloride.

6. 4-ethoxybutyl bis(hydroxymethyl)propylphosphonium chloride.

7. A method which comprises bringing into reactive contact in the temperature range of 20 C. to 100 C., in the presence of a member selected from the group consisting of water and a lower alkyl alcohol, a base selected from the group consisting of the oxides, hydroxides, lower alkoxides and carbonates of alkali metals and alkaline earth metals and strongly basic organic tertiary amines selected from the group consisting of tertiary alkyl amines, tertiary aralkyl amines and tertiary heterocyclic amines, and a hydroxymethyl phosphonium salt of the formula and recovering the corresponding hydroxymethyl phosphine having the formula said base being present in the reaction mixture in about a stoichiometric quantity throughout substantially all of the reaction; R and R in the above formulae each represent a member selected from the group consisting of alkyl having from 1 to 20 carbon atoms; substituted alkyl having from 1 to 20 carbon atoms; alkenyl having from 2 to 20 carbon atoms; said substituents for alkyl being selected from the group consisting of cyano, and lower alkoxy; cyclohexyl; hydroxy-substituted cyclohexyl; cyclohexenyl; phenyl; substituted phenyl; said substituents for phenyl being selected from the group consisting of lower alkoxy, lower alkyl, and halo; Y is a mineral acid residue; x is selected from and 1; and y is selected from 0 and 1.

8. A method which comprises bringing tetrakis-(hydroxymethyl)phosphonium chloride into reactive contact in the temperature range of -20 C. to 100 C., in the presence of a member selected from the group consisting of water and a lower alkyl alcohol, with a base selected from the group consisting of the oxides, hydroxides, lower alkoxides and carbonates of alkali metals and alkaline earth metals and strongly basic organic tertiary amines selected from the group consisting of tertiary alkyl amines, tertiary aralkyl amines and tertiary heterocyclic amines, said base being present in the reaction mixture in about a stoichiometric quantity throughout substantially all of the reaction, and recovering tris(hydroxymethyl)phosphine.

9. A method which comprises bringing bis(hydroxy' methyl)diphenylphosplronium chloride into reactive contact in the temperature range of 20 C. to C., in the presence of a member selected from the group consisting of water and a lower alkyl alcohol, with a base selected from the group consisting of the oxides, hydroxides, lower alkoxides and carbonates of alkali metals and alkaline earth metals and strongly basic organic tertiary amines selected from the group consisting of tertiary alkyl amines, tertiary aralkyl amines and tertiary heterocyclic amines, said base being present in the reaction mixture in about a stoichiometric quantity throughout sub- .stantially all of the reaction, and recovering (hydroxymethyl) diphenylphosphine.

10. A method which comprises bringing cyclohexyltris(hydroxymethyl)phosphonium chloride into reactive contact in the temperature range of -20 C. to 100 C., in the presence of a member selected from the group consisting of water and a lower alkyl alcohol, with a base selected from the group consisting of the oxides, hydroxides, lower alkoxides and carbonates of alkali metals and alkaline earth metals and strongly basic organic tertiary amines selected from the group consisting of tertiary alkyl amines, tertiary aralkyl amines and tertiary heterocyclic amines, said base being present in the reaction mixture in about a stoichiometric quantity throughout substantially all of the reaction, and recovering cyclohexylbis (hydroxymethyl phosphine.

11. The process of claim 7 wherein the base is added to the hydroxymethyl phosphonium salt reactant.

12. The process of claim 7 wherein the base is an alkali metal hydroxide.

13. The process of claim 7 wherein the base is an alkaline earth metal oxide.

14. The process of claim 7 wherein the base is a lower alkali metal alkoxide.

15. The process of claim 7 wherein the base is a strongly basic organic tertiary amine selected from the group consisting of tertiary alkyl amines, tertiary aralkyl amines and tertiary heterocyclic amines.

No references cited.

CHARLES B. PARKER, Primary Examiner.

JOSEPH P. BRUST, Assistant Examiner. 

1. A HYDROXYMETHYLPHOSPHINE HAVING THE FORMULA
 7. A METHOD WHICH COMPRISES BRINGING INTO REACTIVE CONTACT IN THE TEMPERATURE RANGE OF -20*C. TO 100*C., IN THE RPESENCE OF A MEMBER SELECTED FROMTHE GROUP CONSISTING OF WATER AND A LOWER ALKYL ALCOHOL, A BASE SELECTED FROM THE GROUP CONSISTING OF THE OXIDES, HYDROXIDES, LOWER ALKOXIDES AND CARBONATES OF ALKALI METALS AND ALKALINE EARTH METALS AND STRONGLY BASIC ORAGNIC TERTIARY AMINES SELECTED FROMTHE GROUP CONSISTING OF TERTIARY ALKYL AMINES, TERTIARY ARALKYL AMINES AND TERTIARY HETEROCYCLIC AMINES, AND A HYDRROXYMETHYL PHOSPHONIUM SALT OF THE FROMULA 